Substituted biphenyloxazolines

ABSTRACT

New pesticidal substituted biphenytoxazolines of the formula (I)                    
     in which 
     A, B, X, m and n have the meanings stated in the description, and new intermediates therefor.

The invention relates to new substituted biphenyloxazolines, to aplurality of processes for their preparation, to new intermediates, andto the use of the substituted biphenyloxazolines for combating animalpests.

It is known that certain substituted biphenyloxazolines, such as2-(2,6-difluorophenyl)-4-(4′-chlorobiphenyl-4)-2-oxazoline, have aninsecticidal and acaricidal activity (cf. EP-A-0 432 661).

However, the level and/or duration of activity of these known compoundsare not entirely satisfactory in all fields of application, inparticular against certain organisms or when low concentrations areapplied.

New substituted biphenyloxazolines of the formula (I)

have been found,

in which

A represents hydrogen, fluoro or chloro,

B represents fluoro or chloro,

in which

R represents R¹ or R², where

R¹ represents halogenoalkyl or halogenocycloalkyl having in each case atleast one fluorine atom and additionally at least one hydrogen orchlorine atom, or represents halogenocycloalkenyl having at least onefluorine atom,

R² represents hydrogen, alkenyl, alkinyl or represents optionallysubstituted cycloalkyl, or represents optionally substitutedcycloalkylalkyl, or represents optionally substituted cycloalkenylalkyl,or represents optionally substituted cycloalkenyl, or representsphenylalkyl or naphthylalkyl, each of which is optionally substituted,represents optionally substituted heteroarylalkyl, or represents theradical COR³,

in which

R³ represents alkyl, alkoxy, alkenyl, alkenyloxy, or representscycloalkyl, cycloalkyloxy or cycloalkylalkyloxy, or cycloalkylalkyloxy,each of which is optionally substituted, or represents phenyl ornaphthyl, each of which is optionally substituted, or represents theradical NR⁴R⁵,

in which

R⁴ represents hydrogen or alkyl and

R⁵ represents alkyl, halogenoalkyl, or represents cycloalkyl orcycloalkylalkyl, each of which is optionally substituted, or representsphenyl or phenylalkyl, each of which is optionally substituted,

X represents halogen, alkyl or alkoxy,

m represents 0, 1 or 2 and

n represents 1 or 2.

Due to one or more chiral centers, the compounds of the formula (I) aregenerally obtained in the form of stereoisomer mixtures. They can beused in the form of their diastereomer mixtures and also as purediastereomers or enantiomers.

Furthermore, it has been found that the new substitutedbiphenyloxazolines of the formula (I) are obtained by a process wherein

A) in a first step, to obtain compounds of the formula (II)

in which

R¹, X, m and n have the abovementioned meanings,

α) to obtain compounds of the formula (IIa)

 in which

W and Y independently of one another represent fluorine, chlorine ortrifluoromethy,

D represents hydrogen or fluorine,

Z represents fluorine or

W and Z together represent -(CF₂)₁

in which

1 represents 2, 3, or 4,

n represents 1 or 2 and

m represents 0, 1 or 2,

a hydroxybiphenyl of the formula (III)

 in which

X, m and n have the abovementioned meanings,

is reacted with a compound of the formula (IV)

 in which

W, Y and Z have the abovementioned meanings,

if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a diluent and, ifappropriate, the product is subsequently hydrogenated,

or

β) to obtain compounds of the formula (IIb)

 in which

X, m and n have the abovementioned meanings,

hydroxybiphenyls of the abovementioned formula (III) are reacted with adifluorohalogenomethane of the formula (V)

CHF₂Hal  (V)

 in which

Hal represents chlorine or bromine,

if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a diluent,

or

γ) to obtain compounds of the formula (IIc)

 in which

X, R¹, m and n have the abovementioned meanings,

aminophenol derivatives of the formula (VI)

 in which

X, R¹, m and n have the abovementioned meanings,

are diazotized and the resulting diazonium salt is reacted with benzenein the presence of acid and iron powder or in the presence of a base andin each case, if appropriate, in the presence of a diluent,

or

δ) to obtain compounds of the formula (IId)

 in which

X, m and n have the abovementioned meanings,

a hydroxybiphenyl of the abovementioned formula (III) is reacted withcarbon tetrachloride in the presence of hydrofluoric acid, ifappropriate in the presence of a diluent,

B) in a second step, to obtain compounds of the formula (VII)

in which

X, R¹, m and n have the abovementioned meanings,

α) the compounds of the formula (II) which can be obtained by process A)are reacted with acetyl chloride in the presence of an acid or Lewisacid and in the presence of a diluent,

or

β) to obtain compounds of the formula (VIIa)

 in which

B, X, m, n, W, Y and Z have the abovementioned meanings,

a hydroxybiphenyl derivative of the formula (IIIa)

 in which

X, m and n have the abovementioned meanings,

is reacted with a compound of the formula (IV)

 in which

W, Y and Z have the abovementioned meanings,

if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a solvent and, ifappropriate, the product is subsequently hydrogenated,

or

γ) to obtain compounds of the formula (VIIb)

 in which

X, m and n have the abovementioned meanings,

a hydroxybiphenyl derivative of the formula (IIIa) shown above isreacted with a difluorohalogenomethane of the formula (V) shown above,if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a diluent,

C) in a third step, to obtain compounds of the formula (VIII)

 in which

X, R¹, m and n have the abovementioned meanings and

Hal represents chlorine or bromine,

α) the compounds of the formula (VII) shown above, which can be obtainedby process B), are chlorinated or brominated, if appropriate in thepresence of a diluent,

or

β) the compounds of the formula (II) shown above, which can be obtainedby process A), are reacted with halogenoacetyl chlorides of the formula(IX)

HalCH₂COCl  (IX)

 in which

Hal represents chlorine or bromine,

in the presence of an acid or Lewis acid and in the presence of adiluent,

D) in a fourth step, to obtain compounds of the formula (X)

in which

X, R¹, m and n have the abovementioned meanings,

the compounds of the formula (VIII) shown above, which can be obtainedby process C), are reacted with a salt of formic acid, in the presenceof a diluent and if appropriate in the presence of a catalyst,

E) in a fifth step, to obtain compounds of the formula (XI)

 in which

X, R¹, m and n have the abovementioned meanings,

the compounds of the formula (X) shown above, which can be obtained byprocess D), are reacted with the compound of the formula (XII)

H₂N—OCH₃  (XII),

 if appropriate in the presence of a diluent,

F) in a sixth step, to obtain compounds of the formula (XIII)

 in which

R¹, X, m and n have the abovementioned meanings,

the compounds of the formula (XI) shown above, which can be obtained byprocess E), are reduced using a reducing agent in the presence of anacid and if appropriate in the presence of a diluent,

G) in a seventh step, to obtain compounds of the formula (XIV)

in which

A, B, R¹, X, m, and n have the abovementioned meanings, either

α) the compounds of the formula (XIII) shown above, which can beobtained by process F), are reacted with 2-A, 6-B- benzoyl chloride ifappropriate in the presence of a base and if appropriate in the presenceof a dituent,

or

β) the compounds of the formula (II) shown above, which can be obtainedby process A), are first reacted with a compound of the formula (XV)

 in which

A and B have the abovementioned meanings,

V represents chlorine, hydroxyl or C₁-C₄-alkoxy and

R⁶ represents hydrogen or alkyl, preferably hydrogen or C₁-C₆-alkyl,

 in the presence of an acidic catalyst and if appropriate in thepresence of a diluent, and

the resulting compounds of the formula (XVI)

 in which

A, B, R¹, X, m, n and R⁶ have the abovementioned meanings,

are reduced by means of a reducing agent in the presence of a diluent,

H) in an eighth step, to obtain compounds of the formula (XVII)

in which

A, B, X, m and n have the abovementioned meanings,

R′ represents R¹ or COR³, in which

R¹ and R3 have the abovementioned meanings

either

α) the compounds of the formula (XIV) shown above, which can be obtainedby process G), are reacted with a chlorinating agent, if appropriate inthe presence of a diluent,

or

β) the compounds of the formula (II) shown above, which can be obtainedby process A), or a compound of the formula (IIe)

 in which

R³, X, n and m have the abovementioned meanings,

are reacted with a compound of the formula (XVIII)

 in the presence of an acidic catalyst and if appropriate in thepresence of a diluent,

and

I) in a ninth step, the compounds of the formula (XVII) shown above,which can be obtained by process H), are cyclized in the presence of abase, if appropriate in the presence of a catalyst and if appropriate inthe presence of a diluent,

and, if appropriate,

J) the compounds of the formula (Ia) obtained for R=COR³

in which

A, B, R³, x, n and m have the abovementioned meanings,

are hydrolysed to give compounds of the formula (Ib)

 in which

A, B, X, n and m have the abovementioned meanings

and, if appropriate, these are subsequently

Kα) reacted with a compound of the formula (XIX)

HalCOR³  (XIX)

 in which

R³ has the abovementioned meaning and

Hal represents halogen, preferably chlorine or bromine, if appropriatein the presence of a diluent and if appropriate in the presence of abase, or

βreacted with a compound of the formula (IV)

 in which

W, Y and Z have the abovementioned meanings,

if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a diluent, and, ifappropriate, the product is subsequently hydrogenated,

or

γ) reacted with a difluorohalogenomethane of the formula (V)

CHF₂Hal  (V)

in which

Hal represents chlorine or bromine,

if appropriate in the presence of a base, if appropriate in the presenceof a catalyst and if appropriate in the presence of a diluent,

or

δ) reacted with carbon tetrachloride in the presence of hydrofluoricacid, if appropriate in the presence of a diluent, or

ε) reacted with a compound of the formula (XX)

M-R²  (XX)

in which

R² has the abovementioned meaning and

M represents a leaving group, if appropriate in the presence of adiluent and if appropriate in the presence of a base.

Furthermore, it has been found that the new substitutedbiphenyloxazolines of the formula (I) are highly suitable for combatinganimal pests, in particular insects, arachnids and nematodes which occurin agriculture, in afforestations, in the protection of stored productsand of materials and in the hygiene field.

Formula (I) provides a general definition of the compounds according tothe invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned hereinabove and hereinbelow are explained below.

A represents hydrogen, fluoro or chloro,

B represents fluoro or chloro,

R preferably represents R¹ or R², where

R¹ represents C₁-C₆-halogenolalkyl or C₃-C₆-halogenoalkyl having in eachcase at least one fluorine atom and additionally at least one hydrogenor chlorine atom, or represents C₄-C₆-halogenocycloalkenyl having atleast one fluorine atom and

R² represents hydrogen C₃-C₁₂-alkenyl, C₃-C₁₂-alkinyl, or representsC₃-C₆-cycloalkyl which is optionally substituted by C₁-C₄-alkyl,C₂-C₄-alkenyl, C₂-C₄-halogenoalkenyl, phenyl, halogenophenyl, styryl orhalogenostyryl,

or represents C₃-C₆-cycloalkyl-C₁-C₄-alkyl which is optionallysubstituted by halogen, C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-halogenoalkenyl, phenyl, halogenophenyl, styryl or halogenostyryl,or represents C₄-C₆-cycloalkenyl-C₁-C₄-alkyl which is optionallysubstituted by halogen or C₁-C₄-alkyl,

or represents C₄-C₆-cycloalkenyl which is optionally substituted byC₁-C₄-alkyl,

or represents phenyl-C₁-C₆-alkyl, naphthyl-C₁-C₃-alkyl ortetrahydronaphthyl- C₁-C₃-alkyl, each of which is optionallymonosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of nitro, halogen, C₁-C₁₂-alkyl,C₁-C₁₂-halogenoalkyl, C₁-C₁₂-alkoxy or C₁-C₁₂- hologenoalkoxy,

or represents 5- or 6-membered heteroaryl-C₁-C₄-alkyl which isoptionally monosubstituted or disubstituted by identical or differentsubstituents from the series consisting of nitro, halogen, C₁-C₁₂-alkyl,C₁-C₁₂-halogenoalkyl, C₁-C₁₂-alkoxy or C₁-C₁₂-halogenoalkoxy and whichhas 1 or 2 identical or different hetero atoms from the seriesconsisting of nitrogen, oxygen and sulfur,

or represents the radical COR³.

R³ preferably C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, C₃-C₁₂-alkenyl, C₃-C₁₂-alkenyloxy, or represents C₃-C₁₀-cycloalkyl, C₃-C₁₀-cycloalkyloxy orC₃-C₁₀- cycloalkyl-C₁-C₆-alkoxy, each of which is optionally substitutedby halogen, C₁-C-alkyl, C₁-C₄-halogenoalkyl, C₂-C₄-alkenyl or C₂-C₄-halogenoalkenyl,

or represents phenyl or naphthyl, each of which is optionallymonosubstituted to tetrasubstituted by identical or differentsubstituents from the series consisting of halogen, C₁-C₁₂- alkyl,C₁-C₁₂-halogenoalkyl, C₁-C₁₂-alkoxy or C₁-C₁₂-halogenoalkoxy, orrepresents the radical NR⁴R⁵.

R⁴ preferably represents hydrogen or C₁-C₁₂-alkyl.

R⁵ represents C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl, or representsC₃-C₁₀-cycloalkyl or C₃-C₁₀-cycloalkyl-C₁-C₆-alkyl, each of which isoptionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl orC₂-C₄- halogenoalkenyl, or represents phenyl or phenyl-C₁-C₆-alkyl, eachof which is optionally monosubstituted to tetrasubstituted by identicalor different substituents from the series consisting of halogen,C₁-C₁₂-alkyl, C₁-C₁₂-halogenoalkyl, C₁-C₁₂-alkoxy,C₁-C₁₂-halogenoalkoxy.

X preferably represents halogen, C₁-C₆-alkyl or C₁-C₁₂-alkoxy.

m preferably represents 0, 1 or 2.

n preferably represents 1 or 2.

A particularly represents hydrogen, fluoro or chloro,

B particularly preferably fluoro or chloro,

R particularly preferably represents R₁ or R₂, where

R¹ represents C₁-C₃-halogenoalkyl or C₄-C₅-halogenocycloalkyl having ineach case at least one fluorine atom and additionally at least onehydrogen or chlorine atom, or represents C₄-C₆-halogenocycloalkenylhaving at least one fluorine atom and

R² represents hydrogen, C₃-C₁₂-alkenyl, C₃-C₅-alkinyl, or representsC₃-C₆-cycloalkyl which is optionally substituted by C₁-C₄-alkyl,C₂-C₄-alkenyl, C₂-C₃-halogenoalkenyl, phenyl, halogenophenyl, styryl orhalogenostyryl,

or represents C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which is optionallysubstituted by halogen, C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₃-halogenoalkenyl, phenyl, halogenophenyl, styryl or halogenostyryl,

or represents C₄-C₆-cycloalkenylmethyl which is optionally substitutedby halogen,

or represents C₄-C₆-cycloalkenyl,

or represents phenyl-C₁-C₆-alkyl, naphthylmethyl,tetrahydronaphthylmethyl, pyridyl-, furanyl-, thiazolyl-, oxazolyl-, orisoxazolyl-C₁-C₃-alkyl, each of which is optionally monosubstituted ordisubstituted by identical or different substituents from the seriesconsisting of nitro, halogen, C₁-C₄-alkyl, C₁-C₄- halogenoalkyl,C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy, or represents the radical COR ³.

R³ particularly preferably represents C₁-C₆-alkyl, C₁-C₆-alkoxy,C₃-C₆-alkenyl, C₃-C₆-alkenyloxy, or represents C₃-C₆-cycloalkyl,C₃-C₆-cycloalkyloxy or C₃-C₆-cycloalkyl-C₁-C₂-alkyloxy, each of which isoptionally substituted by fluorine, chlorine, C₁-C₃-alkyl,C₁-C₂-halogenoalkyl or C₂-C₃-halogenoalkenyl or represents phenyl whichis optionally monosubstituted or disubstituted by identical or differentsubstituents from the series consisting of halogen, C₁-C₄-alkyl,C₁-C₃-halogenoalkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy, or representsthe radical NHR⁵.

R⁵ particularly preferably represents C₁-C₄-alkyl, phenyl or benzyl eachof which is optionally monosubstituted or disubstituted by identical ordifferent substituents from the series consisting of fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl or C₁-C₄-halogenoalkoxy.

X particularly preferably represents fluorine, chlorine or bromine.

m particularly preferably represents 0 or 1.

n particularly preferably represents 1.

A very particularly preferably represents hydrogen, fluoro or chloro,

B very particularly preferably represents fluoro or chloro,

R very particularly preferably represents R₁ or R₂, where

R¹ represents one of the groups —CHF₂, —CCIF₂, —CF₂CHFCI, —CF₂CH₂F,—CF₂CHF₂, —CF₂CCI₃, —CF₂CHFCF₃, —CH₂CF₃, —CH₂CF₂CHF₂, —CH₂CF₂CF₃,

R² represents hydrogen, or represents propenyl, butenyl, pentenyl,hexenyl, propinyl, butinyl, pentinyl,

or represents one of the cycloalkylalkyl groups:

 or represents the cycloalkenylalkyl group:

 or represents one of the phenylalkyl groups:

or represents

or represents one of the heteroarylalkyl groups:

or represents the radical —COR³

R³ very particularly preferably represents methyl, ethyl, propyl;

or represents methoxy, ethoxy, propoxy, butoxy;

or represents cyclopropyl, cyclohexyl;

or represents cyclohexyloxy;

or represents phenyl, 2-chlorophenyl, 3-chlorophenyl,2,6-difluororophenyl, 2-trifluoromethoxyphenyl,4-trifluoromethoxyphenyl; 2,4-dichlorophenyl; 3,4-dichlorophenyl;

or represents the radical -NHR⁵.

R⁵ very particularly preferably represents methyl, ethyl, or representsphenyl which is optionally monosubstituted by chlorine.

X very particularly preferably represents fluorine, chlorine or bromine.

m very particularly preferably represents 0 or 1.

n very particularly preferably represents 1.

Other preferred compounds are those of the formula (Ic)

in which

R, X and m have the abovementioned general, preferred, particularlypreferred or very particularly preferred meanings.

Other preferred compounds are those of the formula (Id)

in which

A represents hydrogen, B represents fluoro and R, X and m have theabovementioned general, preferred, particularly preferred or veryparticularly preferred meanings.

Other preferred compounds are those of the abovementioned formula (Id),in which A represents hydrogen, B represents chloro and R, X and m havethe abovementioned general, preferred, particularly preferred or veryparticularly preferred meanings.

The hydrocarbon radicals, such as alkyl or alkenyl, which have beenmentioned above in in the definition of the compounds according to theinvention, also in connection with hetero atoms such as alkoxy, are, asfar as possible, in each case straight-chain or branched.

The abovementioned definitions of radicals or explanations, in generalor where preferred ranges have been mentioned, can be combined with eachother as desired, that is to say that combinations between therespective ranges and preferred ranges are also possible. They applyanalogously to the end products and to the precursors and intermediates.

Preferred according to the invention are those compounds of the formula(I) in which the meanings mentioned above as being preferred(preferable) are combined.

Particularly preferred according to the invention are those compounds ofthe formula (I) in which the meanings mentioned above as beingparticularly preferred are combined.

Very particularly preferred according to the invention are thosecompounds of the formula (I) in which the meanings mentioned above asbeing very particularly preferred are combined.

If, for example, 4-hydroxybiphenyl and trifluorochloroethylene are usedas starting substances in accordance with process Aα), the course of theprocess according to the invention can be represented by the followingequation:

If, for example, 4-hydroxybiphenyl and difluorobromomethane are used asstarting substances in accordance with process Aβ), the course of theprocess according to the invention can be represented by the followingequation:

If, for example, 4-difluoromethoxyaniline is used as starting substancein accordance with process Aγ), the course of the process according tothe invention can be represented by the following equation:

If, for example, 4-hydroxybiphenyl is used as starting substance inaccordance with process Aδ), the course of the process according to theinvention can be represented by the following equation:

If, for example, 4-difluorochloromethoxybiphenyl is used as startingsubstance in accordance with process Bα), the course of the processaccording to the invention can be represented by the following equation:

If, for example, 4-acetyl-4′-hydroxybiphenyl and hexafluorocyclobuteneare used as starting substances in accordance with process Bβ), thecourse of the process according to the invention can be represented bythe following equation:

If, for example, 4-acetyl-4′-hydroxybiphenyl and chlorodifluoromethaneare used as starting substances in accordance with process Bγ), thecourse of the process according to the invention can be represented bythe following equation:

If, for example, 4-acetyl-4′-difluoromethoxybiphenyl is used as startingsubstance in accordance with process Cα), the course of the processaccording to the invention can be represented by the following equation:

If, for example, 4-difluorochloromethoxybiphenyl and chloroacetylchloride are used as starting substances in accordance with process Cβ),the course of the process according to the invention can be representedby the following equation:

If, for example, 4-chloroacetyl-4′-difluoromethoxybiphenyl is used asstarting substance in accordance with process D), the course of theprocess according to the invention can be represented by the followingequation:

If, for example, 4-hydroxyacetyl-4′-difluorochloromethoxybiphenyl isused as starting substance in accordance with process E), the course ofthe process according to the invention can be represented by thefollowing equation:

If, for example, 4-hydroxyacetyl-oxime O-methyl ether4′-trifluorochloroethoxybiphenyl is used as starting substance inaccordance with process F), the course of the process according to theinvention can be represented by the following equation:

If, for example,2-amino-2-(4′-difluorochloromethoxybiphenyl)-4)-ethan-1-ol is used asstarting material in accordance with process Gα), the course of theprocess according to the invention can be represented by the followingequation:

If, for example, N-(carboxymethylchloromethyl)-2,6-difluorobenzamide and4-difluorochloromethoxybiphenyl are used as starting substances inaccordance with process Gβ), the course of the process according to theinvention can be represented by the following equation:

If, for example,N-(1-(4′-difluoromethoxybiphenyl-4)-ethyl-2-ol)-2,6-difluorobenzamideand thionyl chloride are used as starting substances in accordance withprocess Hα), the course of the process according to the invention can berepresented by the following equation:

If, for example, N-1-methoxy-2-chloroethyl)-2,6-difluorobenzamide and4-difluoromethoxybiphenyl are used as starting substances in accordancewith process Hβ), the course of the process according to the inventioncan be represented by the following equation:

If, for example,N-(1-(4′-difluoromethoxybiphenyl-4-)2-chloroethyl)-2,6-difluorobenzamnideis used as starting substance in accordance with process I), the courseof the process according to the invention can be represented by thefollowing equation

If, for example,2-(2,6-difluorophenyl)-4-(4′-tert-butylcarbonyloxybiphenyl-4)-2-oxazolineis used as starting compound in accordance with process J), the courseof the process according to the invention can be represented by thefollowing equation:

If, for example,2-(2,6-difluorophenyl)-4-(4′-hydroxybiphenyl-4)-2-oxazoline and ethylchloroformate are used as starting compounds in accordance with theprocess Kα), the course of the process according to the invention can berepresented by the following equation:

If, for example,2-(2,6-difluorophenyl)-4-(4′-hydroxybiphenyl-4)-2-oxazoline, andtrifluorochloroethylene are used as starting substances in accordancewith process Kβ), the course of the process according to the inventioncan be represented by the following equation:

If, for example,2-(2,6-difluorophenyl)-4-(4′-hydroxybiphenyl-4)-2-oxazoline anddifluorochloromethane are used as starting substances in accordance withExample Kγ), the course of the process according to the invention can berepresented by the following equation:

If, for example,2-(2,6-difluorophenyl)-4-(4′-hydroxybiphenyl-4)-2-oxazoline and carbontetrachloride are used as starting substances in accordance with ExampleKδ) , the course of the process according to the invention can berepresented by the following equation:

If, for example,2-(2,6-difluorophenyl)-4-(4′-hydroxybiphenyl-4)-2-oxazoline and allylbromide are used as starting substances in accordance with Example Kε),the course of the process according to the invention can be representedby the following equation:

The compounds of the formula (III), which are required as startingsubstances for carrying out process Aα) according to the invention, areknown and/or can be prepared in a simple manner by known methods.

For example, the compounds of the formula (III) are obtained bysulfonating optionally substituted biphenyls and then reacting theproduct with alkali metal hydroxides to give the hydroxybiphenyls, or bydiazotizing aminobiphenyls and boiling the product (cf., for example,Houben-Weyl, Volume VI/1c (1976), pages 216 and 251).

The compounds of the formula (IV) which are furthermore required asstarting substances for carrying out the processes Aα), Bβ)and Kβ)according to the invention are known and/or can be prepared in a simplemanner by known methods (cf., for example, Houben-Weyl, Volume V/3(1962), page 187 et seq., 317, 346 et seq. and 377 et seq.)

The difluorohalogenomethanes of the formula (V) which are required asstarting substances for carrying out the processes Aβ) and Kγ) accordingto the invention are generally known compounds of organic chemistry.

The compounds of the formula (VI) which are required as startingsubstances for carrying out process Aγ) according to the invention areknown and/or can be prepared in a simple manner by known methods.

The compounds of the formula (VI) are obtained for example by reducingthe corresponding nitroaromatics or by subjecting the correspondingcarboxamides e.g. to a Hofmann degradation.

The halogenoacetyl chlorides of the formula (IX) which are required asstarting substances for carrying out process Cβ) according to theinvention are conventional, generally known chemicals of organicchemistry.

The compound (XII) which is required for carrying out process E)according to the invention is a generally known chemical of organicchemistry.

The compounds of the formula (XV) which are required as startingsubstances for carrying out process Gβ) according to the invention areknown and/or can be prepared in a simple manner by known methods (cf.,for example, WO 93/24 470).

The compounds of the formula (XVIII) which are required as startingsubstances for carrying out process Hp) according to the invention areknown and/or can be prepared in a simple manner by known methods (cf.,for example, EP-A-0 594 179). The compounds of the formula (IIe) whichare also required as starting substances for carrying out process Hβ)according to the invention are known and/or can be obtained in a simplemanner, for example by acylating the corresponding hydroxybiphenyls.

The compounds of the formula (XIX) which are required as startingsubstances for carrying out process Kα) according to the invention aregenerally known compounds of organic chemistry.

The compounds of the formula (XX) which are required as startingsubstances for carrying out process Kε) according to the invention aregenerally known compounds of organic chemistry.

M represents a customary leaving group; if R² has the meaning —COR³ Mpreferably represents halogen, such as, in particular, chlorine orbromine, anhydride and imidazolide; if R² has the other above mentionedmeanings M preferably represents halogen, such as, in particular,chlorine or bromine; alkylsulfonyloxy, such as, in particular,methylsulfonyloxy; and optionally substituted arylsulfonyloxy, such as,in particular, phenylsulfonyloxy, p-chlorophenylsulfonyloxy ortolylsulfonyloxy.

The intermediates of the formulae (Ia), (Ib), (II), (IIa), (IIb), (IIc),(IId), (VII), (VIIa), (VIb), (VIII), (X), (XI), (XIII), (XIV), (XVI) and(XVII) are new and also subject of the invention. They themselves haveinsecticidal and acaricidal properties in some cases, for example thecompounds of the formula (Ia), (Ib), (XIV) and (XVII).

Process Aα) for the preparation of compounds of the formula (IIa)comprises a process in which compounds of the formula (III) are reactedwith compounds of the formula (IV), if appropriate in the presence of abase, if appropriate in the presence of a catalyst and if appropriate inthe presence of a diluent, and, if appropriate, the product issubsequently hydrogenated.

Diluents which can be employed are all customary solvents. Substanceswhich can preferably be used are, for example, nitrites, such asacetonitrile and butyronitrile, or ethers, such as methyl tert-butylether, methyl tert-amyl ether, diisopropyl ether, 1,2-dimethoxyethane,tetrahydrofuran and dioxane.

Bases which can be employed are all customary proton acceptors. Exampleswhich may be mentioned are tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU), aswell as alkali metal hydroxides and alkaline earth metal hydroxides.Substances which can preferably be used are alkali metal hydroxides, inparticular sodium hydroxide or potassium hydroxide, all of which canalso be employed in the form of an aqueous solution.

Phase transfer catalysts may be employed as catalysts. Examples whichmay be mentioned are quaternary ammonium salts, such astetraoctylammonium bromide and benzyltriethylammonium chloride.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between 20° C. and100° C., preferably between 25° C. and 70° C.

In general, the reaction is carried out under atmospheric pressure orelevated pressure. In general, the process is carried out under apressure of between 1 bar and 25 bar, preferably between 1 bar and 6bar.

The ratio of base to starting substance of the formula (III) can bevaried within a substantial range. In principle, catalytic amounts ofbase suffice, but the base can also be employed in equimolar amounts orin excess. In general, 0.1 to 5 mol, preferably 0.5 to 2 mol, of baseare used per mole of compound of the formula (III).

In general, the procedure is followed in which the compound of theformula (III) and the base are introduced into a diluent, the reactiontemperature desired is set, and an approximately equimolar amount of theolefin of the formula (IV) is metered in.

If the process is carried out in a sealed vessel or in an autoclave, acertain inherent pressure is established, and this pressure can beelevated by passing in an inert gas such as, for example, nitrogen.

The reaction mixture is worked up in the customary manner, for exampleby extraction or filtration.

Open-chain compounds of the formula (IV) react with the compounds of theformula (III) by an addition reaction.

Cyclic compounds of the formula (IV) react with the compounds of theformula (III) at the double bond by a substitution reaction. The doublebond which then remains can subsequently be hydrogenated, ifappropriate, for example using hydrogen (if appropriate under elevatedpressure) in the presence of a noble metal catalyst such as, forexample, platinum or palladium. The hydrogenation is preferably carriedout in a diluent, suitable diluents being all customary solvents suchas, for example, (halogeno)hydrocarbons, ethers and alcohols. If Yrepresents fluorine or chlorine, it is preferred to use aproticsolvents.

Process Aβ) for the preparation of compounds of the formula (IIb)comprises a process in which compounds of the formula (III) are reactedwith a difluorohalogenomethane of the formula (V), if appropriate in thepresence of a base, if appropriate in the presence of a catalyst and ifappropriate in the presence of a diluent.

Diluents which can be employed are all customary solvents. Substanceswhich can preferably be used are, for example, nitriles, such asacetonitrile and butyronitrile, ethers, such as methyl tert-butyl ether,methyl tert-amyl ether, dilsopropyl ether, 1,2-dimethoxyethane,tetrahydrofuran and dioxane, or alcohols, such as ethanol, the propanolisomers or the butanol isomers.

Bases which can be employed are all customary proton acceptors. Thefollowing can preferably be used: alkali metal hydroxides, such assodium hydroxide or potassium hydroxide, all of which can also beemployed in the form of an aqueous solution.

Phase transfer catalysts may be employed as catalysts. Examples whichmay be mentioned are quarternary ammonium salts, such astetraoctylammonium bromide and benzyltriethylammonium chloride, andphosphonium salts, such as tetrabutylphosphonium bromide.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at a temperature between 20° C. and150° C., preferably between 40° C. and 100° C.

In general, the reaction is carried out under atmospheric pressure orelevated pressure. In general, the process is carried out under apressure of between 1 bar and 25 bar, preferably between 1 bar and 10bar.

The ratio of base to starting substance of the formula (III) can bevaried within a substantial range. In general, 1 to 10 mol, preferably 1to 5 mol, of base are employed per mole of compound of the formula(III).

The difluorohalogenomethane of the formula (V) is generally employed inup to 5-fold excess.

Process Aγ) for the preparation of compounds of the formula (IIc)comprises a process in which compounds of the formula (VI) arediazotized and the product is reacted with benzene in the presence ofacid and iron powder or in the presence of a base and, if appropriate,in the presence of a diluent.

Suitable diluents are all inert solvents. Alternatively, a larger excessof the reactant benzene, preferably up to 30 mol, particularlypreferably up to 5 mol, per mole of the compound of the formula (VI),may be used as the diluent.

If the reaction is carried out in the presence of acid and iron powder,then suitable acids are preferably organic acids such as trichloroaceticacid.

If the reaction is carried out in the presence of a base, suitable basesare, for example, salts of organic acids such as alkali metal acetates,in particular sodium acetate or potassium acetate.

In general, two equivalents of base are employed.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at a temperature between −40° C. and140° C., preferably between −20° C. and 80° C.

The reaction is generally carried out under atmospheric pressure.

The diazonium salt is generally prepared from the compound of theformula (VI) in the presence of an acid, such as hydrochloric acid orsulfuric acid, in a customary manner by reaction with an alkali metalnitrite, such as sodium nitrite, or an alkyl nitrite, such as pentylnitrite or methyl nitrite, or by reaction with nitrosyl chloride.

The reaction mixture comprising the product of the formula (IIc) isworked up with the aid of customary methods.

Process Aδ) for the preparation of compounds of the formula (IId)comprises a process wherein compounds of the formula (III) are reactedwith carbon tetrachloride in the presence of anhydrous hydrofluoricacid, if appropriate in the presence of a diluent.

Suitable diluents are inert organic solvents. An excess of 2 to 3 timesthe amount of carbon tetrachloride is preferably used as diluent.

The amount of anhydrous hydrofluoric acid can be varied within asubstantial range. In general, 2 to 40 mol, preferably 5 to 20 mol. ofanhydrous hydrofluoric acid are employed per mole of the compound of theformula (III).

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at a temperature between 60° C. and150° C., preferably between 80° C. and 125° C.

In general, a procedure is followed in which, in an autoclave, thecompound of the formula (III) is mixed with carbon tetrachloride andanhydrous hydrofluoric acid, and the mixture is heated to the desiredtemperature and stirred at the prevailing pressure.

For working-up, the reaction mixture is freed from components of highervolatility, such as hydrofluoric acid, freons and excess carbontetrachloride, for example by means of distillation.

The residue is taken up in a suitable inert solvent, and the mixture iswashed with alkali and purified by distillation.

Process Bα) for the preparation of compounds of the formula (VII)comprises a process in which compounds of the formula (II) are reactedwith acetyl chloride in the presence of an acid or Lewis acid and in thepresence of a diluent.

Suitable diluents are all customary solvents which are suitable forFriedel-Crafts reactions. Chlorinated hydrocarbons such as, for example,methylene chloride or dichloroethane are preferably used.

Suitable acids or Lewis acids are all those which are suitable forFriedel-Crafts reactions. Aluminum chloride, anhydrous hydrofluoricacid, tetrafluoroboric acid or BF₃ etherate are preferably used.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −30° C. and80° C., preferably between −15° C. and 50° C.

The reaction is generally carried out under atmospheric pressure orunder elevated pressure.

Acetyl chloride and the compounds of the formula (II) are generallyemployed in approximately equimolar amounts.

When the reaction has ended, the product is worked up with the aid ofcustomary methods.

Process Bβ) for the preparation of compounds of the formula (VIIa)comprises a process in which compounds of the formula (IIIa) are reactedwith a compound of the formula (IV), if appropriate in the presence of abase, if appropriate in the presence of a catalyst and if appropriate inthe presence of a diluent, and, if appropriate, the mixture issubsequently hydrogenated.

As regards base, catalyst, diluent and the other reaction conditions,what has been said in process Aα) applies equally to the presentprocess.

Process Bγ) for the preparation of compounds of the formula (VIIb)comprises a process in which a compound of the formula (IIIa) is reactedwith a compound of the formula (V), if appropriate in the presence of abase, if appropriate in the presence of a catalyst and if appropriate inthe presence of a diluent.

As regards base, catalyst, diluent and the other reaction conditions,what has been said in process Aβ) applies equally to the presentprocess.

Process Cα) for the preparation of compounds of the formula (VIII)comprises a process in which compounds of the formula (VIII) arechlorinated or brominated, if appropriate in the presence of a diluent.

Suitable diluents are all the solvents which are inert to chlorine andbromine. Examples of diluents which are preferably used arechlorohydrocarbons, such as methylene chloride, chloroform or carbontetrachloride, or alcohols such as methanol or ethanol.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at a temperature between −30° C. and50° C., preferably between −10 C. and 25° C.

The reaction is generally carried out under atmospheric pressure.

In general, a procedure is followed in which the compound of the formula(VII) is introduced into a suitable diluent, and an approximatelyequimolar amount of chlorine or bromine is then metered in at thetemperature desired. It is also possible to employ a small excess, or aslightly substoichiometric amount, of halogen.

Process Cβ) for the preparation of compounds of the formula (VIII)comprises a process in which compounds of the formula (II) are reactedwith halogenoacetyl chlorides of the formula (IX) in the presence of anacid or Lewis acid and in the presence of a diluent.

Suitable diluents are all customary solvents which are suitable forFriedel-Crafts reactions. Chlorinated hydrocarbons such as, for example,methylene chloride or dichloroethane are preferably used.

Suitable acids or Lewis acids are all those which are suitable forFriedel-Crafts reactions. Aluminum chloride or tetrafluoroboric acid arepreferably used.

The temperature can be varied within a substantial range. In general,the process is carried out between −30° C. and 50° C., preferablybetween −15° C. and 30° C.

The reaction is generally carried out under atmospheric pressure.

In general, the hatogenoacetyl chloride of the formula (IX) and thecompound of the formula (II) are employed in approximately equimolaramounts.

When the reaction is complete, the product is worked up with the aid ofcustomary methods. Process D) for the preparation of compounds of theformula (X) comprises a process wherein compounds of the formula (VIII)are reacted with a salt of formic acid, if appropriate in the presenceof a catalyst.

Suitable diluents are all customary solvents which are inert under thereaction conditions. The following can preferably be used: hydrocarbons,such as toluene, xylene, mesitylene, cyclohexane, methylcyclohexane,chlorohydrocarbons, such as chlorobenzene, o-dichlorobenzene, carbontetrachloride, alcohols, such as methanol, ethanol, the propanolisomers, the butanol isomers and the pentanol isomers, ethers, such asdiisopropyl ether, tetrahydrofuran, dioxane, nitrites, such asacetonitrile and butyronitrile, amides, such as dimethylformamide, andalso strongly polar solvents, such as dimethyl sulfoxide and sulfolane.

If appropriate, the abovementioned diluents can also be used in the formof a mixture with water, if appropriate in the presence of a phasetransfer catalyst, e.g. quaternary ammonium salts, such astetraoctylammonium bromide or benzyltriethylammonium chloride.

Salts of formic acid which can preferably be used are sodium formate andpotassium formate.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between 50° C. and200° C., preferably between 80° C. and 160° C.

In general, a procedure is followed in which the compound of the formula(VIII) is heated with 1 to 20 mol, preferably 1 to 5 mol, of formate ina diluent, then, if appropriate, water is added, and the phases areseparated and the diluent is distilled off.

Process E for the preparation of compounds of the formula (XI) comprisesa process wherein compounds of the formula (X) are reacted with thecompound of the formula (XII), if appropriate in the presence of adiluent.

Suitable diluents are all customary solvents. Examples of diluents whichare preferably used are alcohols, such as methanol, ethanol, thepropanol, butanol and pentanol isomers, or ethers, such as diisopropylether, tetrahydrofuran or dioxane, all of which can, if appropriate, beemployed in the form of a mixture with water.

O-methylhydroxylamine, of the formula (XII), can be employed in the formof the free base or else as the salt of an acid. In the latter case, theprocess is carried out in the presence of a base, preferably sodiumacetate. The compound of the formula (XII) is generally employed inequimolar amounts.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and100° C., preferably between 0° C. and 60° C.

The reaction is generally carried out under atmospheric pressure.

Working-up is carried out in the customary manner, for example byfiltration or extraction.

Process F) for the preparation of compounds of the formula (XIII)comprises a process wherein the compound of the formula (XI) is reactedwith a reducing agent in the presence of an acid and, if appropriate, inthe presence of a diluent.

Suitable diluents are all solvents which are inert to the reactants.Diluents which are preferably used are ethers such as, for example,diisopropyl ether, methyl tertbutyl ether, tetrahydrofuran,1,2-dimethoxyethane and dioxane.

The preferred reducing agent is sodium boranate used in an equimolaramount or in excess.

The preferred acid is trifluoroacetic acid used in an equimolar amountor in excess.

The reaction temperature can be varied within a substantial range. Ingeneral, the beginning of the reaction is carried out at temperaturesbetween 0° C. and 50° C., and the temperature is raised during thecourse of the reaction, if appropriate to up to 120° C.

The reaction is generally carried out under atmospheric pressure.

Working-up is carried out with the aid of customary methods.

The reaction product of the formula (XIII) is preferably isolated in theform of salts, for example the hydrochlorides.

Process Gα) comprises a process in which the compound of the formula(XIII) is reacted with 2-A, 6-B- benzoyl chloride, if appropriate in thepresence of a base and if appropriate in the presence of a diluent.

Diluents which can be employed are all solvents which are inert to thesecompounds. The following can preferably be used: hydrocarbons, such asbenzine, benzene, toluene, xylene and tetralin, furthermorehalogenohydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones,such as acetone and methyl isopropyl ketone, furthermore ethers, such asdiethyl ether, tetrahydrofuran and dioxane, in addition carboxylates,such as ethyl acetate, and also strongly polar solvents, such asdimethyl sulfoxide and sulfolane. The reaction can also be carried outin the presence of water if the acid halide is sufficiently stable tohydrolysis.

Suitable bases in the reaction are all customary acid acceptors. Thefollowing can preferably be used: tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), H{umlaut over(u)}nig base and N,N-dimethyl-aniline, furthermore alkaline earth metaloxides, such as magnesium oxide and calcium oxide, moreover alkali metalcarbonates and alkaline earth metal carbonates, such as sodiumcarbonate, potassium carbonate and calcium carbonate, and alkali metalhydroxides or alkaline earth metal hydroxides, such as sodium hydroxideor potassium hydroxide.

The reaction temperatures can vary within a substantial range. Ingeneral, the reaction is carried out at temperatures between −20° C. and+100° C., preferably between 0° C. and 30° C.

The reaction is generally carried out under atmospheric pressure.

When carrying out the process, the starting substances of the formula(XIII) and 2,6-difluorobenzoyl chloride are generally employed inapproximately equivalent amounts. However, it is also possible to employthe carboxylic acid halide in a larger excess (up to 5 mol). Working-upis carried out by customary methods.

Process Gβ) for the preparation of the compound of the formula (XIV)comprises a process wherein (Step 1) the compound of the formula (II) isfirst reacted with a compound of the formula (XV) in the presence of anacidic catalyst and if appropriate in the presence of a diluent and then(Step 2) the resulting compound of the formula (XVI) is reacted with areducing agent in the presence of a diluent.

Suitable diluents for the first step are all solvents which are inert tothe reactants.

The following are preferably used: hydrocarbons such as toluene, xylene,tetralin, halogenohydrocarbons such as methylene chloride, chloroform,chlorobenzene, o-dichlorobenzene, ethers such as diisopropyl ether,methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane,ketones such as acetone or methyl ethyl ketone, alcohols such asmethanol, ethanol and propanol, amides such as dimethylformamide, andsulfoxides such as dimethyl sulfoxide.

Acidic catalysts which are suitable are, in principle, all inorganic ororganic acids or Lewis acids. Examples of acids which are preferablyused are sulfuric acid, methanesulfonic acid, benzenesulfonic acid,aluminum chloride, titanium tetrachloride, phosphorus oxychloride, borontrifluoride etherate. If appropriate, an excess of acid can also act asdiluent.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and150° C., preferably between 0° C. and 50° C.

The reaction is generally carried out under atmospheric pressure.

The compound of the formula (II) and the compound of the formula (XV)are generally employed in equimolar amounts, but it is also possible touse an excess of one or the other compound.

Suitable diluents in the second step are, in particular, alcohols andethers. Examples which may be mentioned are methanol, ethanol, thepropanol, butanol and pentanol isomers, furthermore diethyl ether,diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane anddimethoxyethane.

The preferred reducing agent used is sodium borohydride in an amount of1 to 5 mol per mole of the compound of the formula (XVI).

If the compound of the formula (XVI) is in the form of an acid (R⁶=H),this acid must be converted into an alkyl ester before the reaction withsodium borohydride is carried out.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between 20° C. and150° C., preferably between 50° C. and 100° C.

The reaction is generally carried out under atmospheric pressure.

The product is worked up with the aid of customary methods.

Process Hα) for the preparation of compounds of the formula (XVII)comprises a process wherein compounds of the formula (XIV) are reactedwith a chlorinating agent, if appropriate in the presence of a diluent.

Suitable diluents are all inert organic solvents. Diluents which arepreferably used are hydrocarbons such as toluene, xylene, hexane,cyclohexane, halogenohydrocarbons such as chlorobenzene, chloroform,methylene chloride and ethers such as diethyl ether, diisopropyl ether,dimethoxyethane, tetrahydrofuran and dioxane.

Suitable chlorinating agents are all reactants which can conventionallybe used for this purpose. Examples which may be mentioned are thionylchloride, phosgene and phosphorus oxychloride, all of which aregenerally employed in at least equimolar amounts.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between 0° C. and120° C., preferably between 20° C. and 100° C.

If appropriate, the reaction is carried out in the presence of a base,in particular a tertiary amine such as, for example, triethylamine orpyridine.

Process Hβ) for the preparation of compounds of the formula (XVII)comprises a process wherein compounds of the formula (II) or (IIe) arereacted with compounds of the formula (XVIII) in the presence of anacidic catalyst and if appropriate in the presence of a diluent.

Suitable diluents are all solvents which are inert to the reactants.

The following are preferably used: hydrocarbons such as toluene, xylene,tetralin, halogenohydrocarbons such as methylene chloride, chloroform,chlorobenzene, o-dichlorobenzene, ethers such as diisopropyl ether,methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane,ketones such as acetone or methyl ethyl ketone, alcohols such asmethanol, ethanol, propanol, amides such as dimethylformamide, andsulfoxides such as dimethyl sulfoxide.

Suitable acidic catalysts are, in principle, all inorganic or organicacids or Lewis acids. Examples of acids which are preferably used aresulfuric acid, methanesulfonic acid, benzenesulfonic acid, anhydroushydrofluoric acid, aluminum chloride, titanium tetrachloride, phosphorusoxychloride or boron trifluoride etherate. If appropriate, an excess ofacid can also act as diluent.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and150° C., preferably between 0° C. and 80° C.

The reaction is generally carried out under atmospheric pressure orunder elevated pressure.

In general, the compounds of the formulae (II) or (IIe) and the compoundof the formula (XVIII) are employed in equimolar amounts; however, it isalso possible to use an excess of one or the other compound.

Process I) for the preparation of the compounds of the formula (I)comprises a process wherein the compounds of the formula (XVII) arecyclized in the presence of a base, if appropriate in the presence of acatalyst and if appropriate in the presence of a diluent.

Suitable diluents are all inert organic solvents. If appropriate, theymay be used in the form of a mixture with water. The following arepreferably used: hydrocarbons such as toluene, xylene, tetralin, hexane,cyclohexane, halogenohydrocarbons such as methylene chloride,chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as methanol,ethanol, glycol, the propanol, butanol and pentanol isomers, ethers suchas diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran,dioxane, nitriles such as acetonitrile or butyronitrile, amides such asdimethylformamide, sulfoxides such as dimethyl sulfoxide, andfurthermore sulfolane. Alcohols are particularly preferably used.

Suitable bases are all customary acid acceptors.

The following can preferably be used: tertiary amines such astriethylamine, pyridine, DABCO, DBU, DBN, N,N-dimethylaniline,furthermore alkaline earth metal oxides such as magnesium oxide andcalcium oxide, in addition alkali metal carbonates and alkaline earthmetal carbonates such as sodium carbonate, potassium carbonate andcalcium carbonate, alkali metal hydroxides such as sodium hydroxide andpotassium hydroxide, furthermore alcoholates such as sodium ethanolateor potassium tert-butylate.

If appropriate, the process is carried out in the presence of a phasetransfer catalyst. Examples of suitable phase transfer catalysts areammonium compounds such as tetraoctylammonium bromide orbenzyltriethylammonium chloride.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −10° C. and150° C., preferably between 0° C. and 100° C.

The reaction is generally carried out under atmospheric pressure.

In general, an equimolar amount of base is employed. However, it is alsopossible to use an excess of base.

Working-up is carried out in the customary manner.

Process J) for the preparation of compounds of the formula (Ib) ischaracterized in that the compounds of the formula (Ia) are hydrolyzed.

Process J) is preferably carried out in the presence of a diluent.Preferred diluents which are used are water/alcohol mixtures, such as,for example, water/methanol, water/ethanol or water/propanol, orwater/amide mixtures such as, for example, water/dimethylformamide (DMF)or water/dimethylacetamide.

Process J) is carried out in the presence of a base. Suitable bases areinorganic and organic bases, in particular alkali metal hydroxides, suchas sodium hydroxide or potassium hydroxide, or ammonia.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −10° C. and60° C., preferably between 0° C. and 40° C. The reaction is generallycarried out under atmospheric pressure.

Process Kα) is characterized in that a compound of the formula (Ib) isreacted with a compound of the formula (XIX), if appropriate in thepresence of a diluent and if appropriate in the presence of a base.

Diluents which can be employed are all solvents which are inert to thesecompounds. The following can preferably be used: hydrocarbons, such asbenzine, benzene, toluene, xylene and tetralin, furthermorehalogenohydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, furthermore ketones,such as acetone and methyl isopropyl ketone, in addition ethers, such asdiethyl ether, tetrahydrofuran and dioxane, moreover carboxylic esters,such as ethyl acetate, and also strongly polar solvents, such asdimethyl sulfoxide and sulfolane. If the acid halide is sufficientlystable to hydrolysis, the reaction can also be carried out in thepresence of water.

Suitable acid-binding agents for the reaction are all customary acidacceptors. The following can preferably be used: tertiary amines, suchas triethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base andN,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, in addition alkali metal carbonatesand alkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and alkali metal hydroxides or alkalineearth metal hydroxides, such as sodium hydroxide or potassium hydroxide.

The reaction temperatures can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and+100° C., preferably between 0° C. and 30° C.

The reaction is generally carried out under atmospheric pressure.

When carrying out the process, the starting substances of the formulae(Ib) and (XIX) are generally used in approximately equivalent amounts.However, it is also possible to employ the compound of the formula (XIX)in a larger excess (up to 5 mol). Working-up is carried out by customarymethods.

Process Kβ) is characterized in that a compound of the formula (Ib) isreacted with a compound of the formula (IV), if appropriate in thepresence of a base, if appropriate in the presence of a catalyst and ifappropriate in the presence of a diluent, and, if appropriate, theproduct is subsequently hydrogenated.

What has been said above for process Aα) with regard to diluent, base,catalyst, temperature, pressure, ratio of base to starting substance ofthe formula (Ib), carrying out the process and working-up the productapplies analogously.

Process Kγ) is characterized in that a compound of the formula (Ib) isreacted with a difluorohalogenomethane of the formula (V), ifappropriate in the presence of a base, if appropriate in the presence ofa catalyst and if appropriate in the presence of a diluent.

What has been said above for process Aβ) with regard to diluent, base,catalyst, temperature, pressure and ratio by weight of the substancesinvolved applies analogously.

Process Kδ) is characterized in that a compound of the formula (Ib) isreacted with carbon tetrachloride in the presence of hydrofluoric acid,if appropriate in the presence of a diluent.

What has been said above for process Aδ) with regard to diluent, amountof hydrofluoric acid, temperature, carrying out the process and workingup the product applies analogously.

Process Kε) is characterized in that a compound of the formula (Ib) isreacted with a compound of the formula (XX), if appropriate in thepresence of a diluent and if appropriate in the presence of a base.

Diluents which are suitable are all customary solvents. The followingcan preferably be used: optionally halogenated, aromatic or aliphatichydrocarbons, ketones, nitriles and amides. Examples which may bementioned are toluene, acetone, acetonitrile, dimethylformamide anddimethylacetamide.

Bases which are suitable are all customary inorganic and organic bases.Examples which may be mentioned are tertiary amines such astriethylamine, DBN, DBU, DABCO, alkali metal hydroxides and alkalineearth metal hydroxides such as, for example, sodium hydroxide, potassiumhydroxide and calcium hydroxide, and also alkali metal carbonates andalkaline earth metal carbonates such as, for example, sodium carbonateor potassium carbonate.

The reaction temperature can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and100° C., preferably between 0° C. and 60° C.

The reaction is generally carried out under atmospheric pressure.

In general, the compounds of the formula (Ib) and the compounds of theformula (XX) are employed in approximately equimolar amounts. However,it is also possible to use an excess of the compounds of the formula(XX).

The active compounds are suitable for combating animal pests, preferablyarthropods and nematodes, in particular insects and arachnids,encountered in agriculture, in forestry, in the protection of storedproducts and of materials, in veterinary medicine and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis, Schistocerca gregaria and Supella spp.

From the order of the Dermaptera, for example, Forficula auricularia.From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Phthirus spp., Pediculus spp., Haematopinus spp.,Linognathus spp. and Solenopotes spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp., Trimenopon spp., Monopon spp., Trinoton spp., Bovicolaspp., Werneckiella spp., Lepikentron spp. and Felicola spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermnedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp. and Panstrongylus spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporanorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilusspp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon soistitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanoglaster, Musca spp., Fannia spp, Calliphoraspp., Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp.,Hyppobosca spp., Stomoxys spp., Oestrus spp;, Hypoderma spp., Tabanusspp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.,Melophagus spp. and Muscina spp.

From the order of the Siphonapterida, for example, Xenopsylla spp.,Ceratophyllus spp., Pulex spp. and Ctenocephalides spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Myocoptes spp., Otodectesspp., Acarus siro, Argas spp., Ornithodoros spp., Ornithonyssus spp.,Dermanyssus spp., Eriophyes ribis, Phyllocoptruta oleivora, Boophilusspp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp.,Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.,Bryobia praetiosa, Panonychus spp., Tetranychus spp., Dermacentor spp.,Haemaphysalis spp., Raillietia spp., Pneumonyssus spp., Sternostormaspp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds according to the invention are distinguished by apowerful insecticidal and acaricidal activity.

They can be particularly successfully to combat insects which areharmful to plants, such as, for example, against the larvae of themustard beetle (Phaedon cochleariae) or against the larvae of the greenrice leafhopper (Nephotettix cincticeps) or against the larvae of thecabbage moth (Plutella maculipennis).

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspoemulsion concentrates,natural and synthetic materials impregnated with active compound, andvery fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents, and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulfoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulfite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas and substances produced bymicroorganisms, inter alia.

Examples of particularly favorable mixture components are the followingcompounds:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichlororo-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulfate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulfide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetylaluminum, fthalide, fuberidazole, furalaxyl, furmecyclox,guazatine,

hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole,iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulfate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl,nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin,piperalin, polycarbamate, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon,

quintozene (PCNEB),

sulfur and sulfur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furanecarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulfate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxin, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazophos, isofenphos, isoprocarb, isoxathion, ivemectin,lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyraclophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozid,tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos,terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,thiomethon, thionazin, thuringiensin, tralomethrin, triarathen,triazophos, triazuron, trichlorfon,

triflumuron, trimethacarb,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides:

for example anilides such as, for example, diflufenican and propanil;arylcarboxylic acids such as, for example, dichloropicolinic acid,dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D,2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones such as, for example, chloridazon andnorflurazon; carbamates such as, for example, chlorpropham, desmedipham,phenmedipham and propham; chloroacetanilides such as, for example,alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlorand propachlor; dinitroanilines such as, for example, oryzalin,pendimethalin and trifluralin; diphenyl ethers such as, for example,acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen andoxyfluorfen; ureas such as, for example, chlortoluron, diuron,fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylaminessuch as, for example, alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imidazolinones such as, for example, imazethapyr,imazamethabenz, imazapyr and imazaquin; nitriles such as, for example,bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example,mefenacet; sulfonylureas such as, for example, amidosulfuron,bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,thifensulfuron-methyl, triasulfuron and tribenuron-methyl;thiocarbamates such as, for example, butylate, cycloate, di-allate,EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate;triazines such as, for example, atrazine, cyanazine, simazine, simetryn,terbutryn and terbutylazine; triazinones such as, for example,hexazinone, metamitron and metribuzin; others such as, for example,aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone,glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,sulfosate and tridiphane.

The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use forms,prepared from these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds, without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention not only act againstplant pests, hygiene pests and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites)such as scaly ticks, Argasidae, scab mites, Trombidae, flies (stingingand sucking), parasitic fly larvae, lice, hair lice, bird lice andfleas. For example, they show an outstanding activity against ticks suchas, for example, Boophilus microplus.

The active compounds of the formula (I) according to the invention arealso suitable for combating arthropods which attack agriculturallivestock such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffalo, rabbits, chikkens, turkeys, ducks, geese,honey bees, other domestic animals such as, for example, dogs, cats,cage birds, aquarium fish, and so-called experimental animals such as,for example, hamsters, guinea pigs, rats and mice. By combating thesearthropods, it is intended to reduce deaths and decreasing performance(in meat, milk, wool, hides, eggs, honey and the like), so that moreeconomical and simpler animal keeping is possible by using the activecompounds according to the invention.

In the veterinary sector, the active compounds according to theinvention are applied in a known manner by means of enteraladministration in the form of, for example, tablets, capsules, drinks,drenches, granules, pastes, boli, the feedthrough method, suppositories,by parenteral administration, such as, for example, by means of aninjection (intramuscular, subcutaneous, intravenous, intraperitoneal andthe like), implants, by means of nasal application, by means of dermalapplication in the form of, for example, immersing or dipping, spraying,pouring-on and spotting-on, washing, dusting, and with the aid of shapedarticles which comprise active compound, such as collars, ear tags, tailmarks, limb bands, halters, marking devices and the like.

When used for cattle, poultry, domestic animals and the like, the activecompounds of the formula (I) can be applied in the form of formulations(for example powders, emulsions, flowables) which comprise 1 to 80% byweight of active compounds, either directly or after diluting them 100to 10,000-fold, or they can be used in the form of a chemical bath.

The preparation and use of the active compounds according to theinvention can be seen from the examples which follow.

PREPARATION EXAMPLES Example (I-1)

6.1 g (0.012 mol) of the compound of Example (XVII-1) are suspended in50 ml of dry methanol. 6.4 g (0.048 mol) of 30% strength sodiumhydroxide solution are added dropwise without cooling, during whichprocess the temperature rises to 27° C. The mixture is heated at theboil for approximately 20 minutes and then cooled. The mixture isfiltered, and the filtrate is washed with water and dried.

Yield: 4.8 g of white crystals (84% of theory) M.p.: 101-103° C.

Example (I-2)

17.6 g (0.042 mol) of2,6-difluoro-N-[2-hydroxyethyl-1-phenyl-4-(4′-difluoromethoxyphenyl)]-benzamideof Example (XIV-1) are suspended in 150 ml of toluene, 20 g (0.168 mol)of thionyl chloride are added dropwise, and the mixture is heated to 70°C. The mixture is held at this temperature for 1.5 hours and thenallowed to cool, and the toluene is distilled off in vacuum. The residueis dissolved in 150 ml of methanol. 22.4 g (0.168 mol) of 30% strengthsodium hydroxide solution are then added, and the mixture is heated for20 minutes at 70° C. After cooling, the mixture is concentrated, theproduct is taken up in methylene chloride, and the mixture is washedthree times with water. Drying and concentrating give 14.9 g of yellowcrystals which are purified over silica gel (petroleum ether/ethylacetate 1:1). 13.0 g of white crystals of m.p. 112° C. are obtained.

Yield: 82% of theory.

The following compounds of the formula (I)

are obtained analogously to Example I-1 or I-2 and in accordance withthe general preparation instructions.

TABLE 1a (n = 1, m = 0) Yield (% of Ex. No. OR M.p. [° C.] theory) I-34-OCF₂CF₂H 106 87 I-4 4-OCF₂CHFCF₃ 86-90 64 I-5 4-OCF₂Cl 115 90 I-6

Example (I-7)

4 ml (0.045 mol) of 50% strength sodium hydroxide solution are addeddropwise at 5° C. to 19.8 g (0.043 mol) of the compound of Example(XVII-3) in 120 ml of dimethylformamide. After 2 hours at roomtemperature, the batch is stirred into 500 ml of ice-water and thecrystals which have precipitated are filtered off with suction.

Yield: 15.1 g (83% of theory), m.p.: 98 to 100° C.

Example (I-8)

10.9 g (0.026 mol) of the compound of Example (I-7) are suspended in 50ml of methanol, and 35.4 ml (0.52 mol) of 25% strength aqueous ammoniasolution are then added dropwise at room temperature. After 28 hours atroom temperature, the precipitate is filtered off with suction andwashed with a little methanol. Yield 7.6 g (97.4% of theory), m.p. 180to 182° C.

Example (I-9) (One-pot reaction in DMF)

9.6 g of the compound of Example (XVII-3) in DMF are treated with sodiumhydroxide solution as described in Example (I7), and the mixture is thenneutralized at 5° C. using dilute hydrochloric acid. After thecorresponding amount of ammonia solution (cf. Example I-8) has beenadded, the mixture is stirred for 15 hours, introduced into ice-waterand filtered off with suction. Yield 7 g (94.5% of theory).

Example (I-10)

Difluorochloromethane is passed for 3 hours at 40 to 50° C. into asolution of 1.2 g (3.4 mmol) of the compound of Example (I-8) and 2.7 g(50 mmol) KOH in 20 ml of isopropanol. After the mixture has cooled, itis poured into 100 ml of ice-water and extracted twice using in eachcase 50 ml of methylene chloride, the extract is dried, the solvent isdistilled off. After chromatography on silica gel using petroleumether/ethyl acetate 1/1 as the eluent, 0.8 g (50% of theory) ofcolorless crystals of m.p. 112° C. is obtained.

Example (I-11)

1.4 ml (0.01 mol) of triethylamine is added to 3.5 g (0.01 mol) of thecompound of Example (I-8), suspended in 20 ml of ethyl acetate, and 1.2g (0.01 mol) of isopropyl chloroformate is then added dropwise in thecourse of 15 minutes, during which process the temperature of thereaction mixture climbs to 30° C. The mixture is stirred for 18 hours atroom temperature and washed with 20 ml of water, the organic phase isdried, and, after concentration, the organic phase is chromatographed onsilica gel using methylene chloride as the eluent. Yield 2.1 g (48% oftheory) m.p. 104° C.

The following compounds of the formula (I)

are obtained analogously or following the general information onpreparation:

TABLE 1b (m = 0, n = 1) Ex. No. OR M.p. [° C.] I-12

118-20 I-13

140-44 I-14* 4-O-nC₄H₉ 102 I-15 4-O—CH₂—C≡CH 128-30 I-16* 4-OCH₃ 124I-17 4-OCH₂—CH═CH—CH₂C(CH₃)₂—CH₂—C(CH₃)₃ oil I-18 4-OCH₂CH═CH—CH₃ 126-128 I-19

110- 112 I-20

129- 130 I-21

143- 145 I-22

195- 197 Fp. [° C.] I-23

78-80 I-24

log P: 5,23 I-25

142 I-26

140- 142 I-27

138- 140 I-28 4-O—(CH₂)₃—C≡CH 105- 108 I-29* 4-O-nC₃H₇ 138- 140 I-30*4-O—CH(CH₃)CH₂CH₃ 50 I-31 4-O—CH₂—CH═CH₂ 130 I-32*

115 I-33*

123 I-34

100- 110 I-35

68 I-36

140-45 *Examples for the use of the compound of Example I-8. ExampleI-37

Example I-38

m.p. 78-81° C. Continuation Ex. No. OR m.p. [° C.] I-394-OCH₂—C(CH₃)═CH₂ 135-138 I-40

90-95 mixture of isomers I-41

152-154 I-42

138-140 I-43

132-134 I-44

126-130 I-45

130-132 I-46

92-95 I-47

180-190 I-48 4-O—CO—NH—C(CH₃)₃ 120-125 I-49

168-171 I-50

118-120 I-51

178-180 Example I-52

PREPARATION OF STARTING COMPOUNDS Example (IIa-1)

250 g of 4-hydroxybiphenyl in 1000 ml of acetone and 50 g of pulverulentsodium hydroxide are introduced into a stirring apparatus equipped atthe bottom of the reaction vessel with a gas inlet tube, and thereaction mixture is heated to the boil. Trifluorochloroethylene issubsequently passed in until the mixture is saturated. After the mixturehas cooled to room temperature, 2000 ml of water are metered in, and theorganic phase which is separating off is removed. After drying, theproduct is distilled; boiling range: 170-174° C./20 mbar. Yield: 295 g.

Example (IIa-2)

250 g of 4-hydroxy-biphenyl, 1000 ml of N-methylpyrrolidone and 50 g ofpulverulent sodium hydroxide are introduced into a stirring apparatusequipped with a gas inlet tube, and the mixture is heated to 130° C.Tetrafluoroethylene is then passed in until no more tetrafluoroethyleneis taken up. After the batch has cooled to room temperature, it isstirred into 3000 ml of water, and the solid is filtered off withsuction, washed with water and dried in vacuo.

391 g of 4-tetrafluoroethoxy-biphenyl=98% of theory are obtained;melting point 65° C.

Example (IIa-3)

Analogously, 250 g of 4-hydroxybiphenyl are reacted withhexafluoropropene to give 4-hexafluoropropoxy-biphenyl.

Yield: 180 g; boiling point: 96-98° C./0.3 mbar, melting point: 60° C.

Example (IIb-1)

51.1 g (0.3 mol) of 4-hydroxybiphenyl are dissolved in 250 ml ofdioxane, and 38.3 ml of 45% strength sodium hydroxide solution areadded. The mixture is heated to 600° C., and 100 g (1.15 mol) ofdifluorochloromethane are then passed in at this temperature. Aftercooling, 75 ml of water are added, the insoluble precipitate is filteredoff with suction, and the aqueous phase is extracted three times usingtert-butyl methyl ether. The combined organic phases are dried andconcentrated. This gives 55.9 g of crude product which still contains20.9% of starting phenol, which is removed using sodium hydroxidesolution.

Yield: 40 g (60% of theory) M.p.: 35° C.

Example (IIe-1)

22 g (0.2 mol) of ethyl chloroformate are added dropwise at 10° C. inthe course of 15 minutes to 34 g (0.2 mol) of 4-hydroxybiphenyl and 28ml of triethylamine in 200 ml of ethyl acetate. Stirring is continuedfor 30 minutes at room temperature, the precipitate is filtered off withsuction, and the liquid phase is washed using 200 ml of water, dried andconcentrated in vacuo, The residue is taken up in 50 ml of diisopropylether and the crystals are filtered off with suction. Yield 47.5 g(98.5% of theory), m.p. 70° C.

Example (Ic-1)

800 ml of benzene, 40 g of Fe powder and 350 g of4-difluoromethoxyaniline are introduced into the reaction vessel, and asolution of 1000 g of trichloroacetic acid in 1600 ml of benzene isadded dropwise at 30-38° C. in the course of 5 hours. At the same time,210 g of sodium nitrite are added in portions (12 g every 15 minutes).The reaction is slightly exothermic, and gas is evolved during theaddition. At the end of the addition, stirring is continued forapproximately 20 hours at room temperature. The mixture is subsequentlyheated up to reflux temperature (75-76° C.) in accordance with theevolution of gas, and stirring is continued until the evolution of gashas ended (approximately 4 hours). The batch is cooled, 2.4 liters of 5%strength hydrochloric acid are added, and benzene is first distilled offuntil the internal temperature has reached 100° C. This is followed bysteam distillation. The organic phase (liquid) is separated off, washedwith water, dried and distilled.

Yield: 109 g, m.p. 55° C. Boiling point: 135-140° C./26 mbar

Example (VII-1)

5.3 g (0.025 mol) of 4-acetyl-4′-hydroxybiphenyl are introduced into 35ml of toluene. 6.7 g (0.075 mol) of 45% strength sodium hydroxidesolution are added dropwise to the suspension at 60° C. 0.42 g (0.00125mol) of tetrabutylphosphonium bromide is subsequently added, and 20 g(0.23 mol) of difluorochloromethane are passed in at 95 to 100° C. inthe course of 2 hours. The mixture is cooled, diluted with water andfiltered (0.4 g). The toluene phase is separated off, and the aqueousphase is extracted twice using toluene. The combined toluene phases arewashed with water, dried and concentrated. This gives 5.9 g (83% oftheory) of beige crystals of m.p. 79-81° C.

Example (VIIa-1)

Trifluorochloroethylene is passed at 40° C. into a mixture of 50 g of4-acetyl-4′-hydroxybiphenyl, 400 ml of acetonitrile, 60 ml of water and10 g of potassium hydroxide until saturation is reached. Theacetonitrile is then removed, and the residue is stirred with 100 ml ofwater. The solid product is filtered off with suction and dried. Thecrude product is subsequently stirred with 20 ml of hot cyclohexane andrefiltered.

Yield: 45 g M.p.: 92-94° C.

Example (VIIa-2)

Analogously to Example (VIIa-1), 96 g of 4-acetyl-4′-hydroxybiphenyl andtetrafluoroethylene give 107 g of crude product, which is dissolved inmethyl tertbutyl ether and extracted using 300 ml of 5% strength sodiumhydroxide solution. The ether phase is concentrated.

Yield: 58 g M.p.: 95-97° C.

Example (VIIa-3)

Analogously to Example (VIIa-1), 50 g of 4-acetyl-4′-hydroxybiphenyl andhexafluoropropene gave 59 g of product.

M.p.: 86-87° C.

Example (VIII-1)

29 g (0.08 mol) of 4-hexafluoropropoxyphenylacetophenone of Example(VIIa-3) are suspended in 200 ml of methanol, and 13.4 g (0.084 mol) ofbromine are added dropwise at 0° C. Stirring is continued for 12 hours,and the mixture is concentrated. This gives 41.3 g of brown crystalswhich are purified on silica gel using methylene chloride as the eluent.Yield: 24.6 g (71% of theory) of yellow crystals of m.p. 69-71° C.

The following compounds of the formula (VIII) are obtained analogouslyand in accordance with the general preparation instructions:

TABLE 2 (m = 0, n = 1) Yield (% of Ex. No. OR Hal M.p. [°C.] theory)VIII-2 4-OCHF₂ Br 83-85 62 VIII-3 4-OCF₂CHFCl Br 72-74 63 VIII-44-OCF₂CF₂H Br 56-61° C. 85

Example (VIII-5)

7 g (0.0525 mol) of aluminum chloride are suspended in 50 ml of1,2-dichloroethane. 5.9 g (0.0525 mol) of chloroacetyl chloride are thenadded dropwise at 5 to 10° C. 13.5 g (0.05 mol) of4-tetrafluoroethoxybiphenyl, dissolved in 10 ml of dichloroethane, arethen added dropwise at −10° C. The mixture is held for a further hour at−10° C., and stirring is then continued for 12 hours at roomtemperature. The reaction mixture is poured into 150 ml of ice-water,ethyl acetate is added, and the organic phase is separated off. This iswashed with bicarbonate solution and then twice with water, dried andconcentrated. The crude product is purified over silica gel (eluentmethylene chloride). This gives 14.7 g of pale beige crystals (yield 85%of theory) of m.p. 74° C.

Example (X-1)

24.3 g (0.055 mol) of bromoketone of Example (VIII-1) are introducedinto 145 ml of ethanol/water. 22.5 g (0.33 mol) of sodium formate areadded to the suspension, and the mixture is heated at the boil for 12hours. Some of the ethanol is distilled off, and the mixture isfiltered. After washing with water and filtration, the product is dried.20.7 g (93% of theory) of crystals of m.p. 135° C. are obtained.

The following compounds of the formula (X) are obtained analogously andin accordance with the general preparation instructions:

TABLE 3 (m = 0, n = 1) Yield [% of the- Ex. No. OR M.p. [°C.] ory) X-24-OCHF₂ 115-18 91 X-3 4-OCF₂CHFCl 160 97 X-4 4-OCF₂CF₂H 155-160 90

Example (XI-1)

5 g (0.018 mol) of 4-difluoromethoxyphenyl-ω-hydroxyacetophenone ofExample (X-2) are dissolved in 50 ml of 1,2-dimethoxyethane, and 5 ml ofwater are added. 1.85 g (0.0225 mol) of sodium acetate and 1.9 g (0.0225mol) of 0-methylhydroxylamine hydrochloride are subsequently added, andthe mixture is stirred overnight at room temperature. The reactionmixture is poured into 180 ml of ice-water and filtered off withsuction, and the product is washed with water and dried. This gives 5.4g of pale beige crystals of m.p. 65-81° C. (E/Z mixture: 43/57).

The following compounds of the formula (XI) are obtained analogously andin accordance with the general preparation instructions:

TABLE 4 (m = 0, n = 1) Yield (% of Ex. No. OR M.p. [°C.] theory) XI-24-OCF₂CHFCl *) 89 XI-3 4-OCF₂CHF₂ *) 83 XI-4 4-OCF₂CHFCF₃ *) 82 *) Sincethe melting range of the resulting E/Z mixtures is very broad, themelting point is not a characteristic value.

Example (XIII-1)

9.2 g (0.2425 mol) of sodium boranate are introduced into 250 ml ofabsolute THF, and 27.6 g (0.2425 mol) of trifluoroacetic acid in 25 mlof THF are then added dropwise at 20° C. in the course of 10 minutes.14.9 g (0.0485 mol) of the oxime ethers of Example (XI-1), dissolved in25 ml of THF, are subsequently added dropwise to the cloudy, colorlessreaction mixture at 15° C. in the course of 15 minutes. The mixture isstirred for 2 hours at room temperature, and stirring is then continuedfor 2 hours at boiling point. After cooling, 150 ml of water arecarefully added at approximately 10° C., and stirring is continued for12 hours at room temperature. The mixture is filtered, and the filtrateis concentrated. After stirring with 2N HCl, the white crystals arefiltered off with suction, washed with methylene chloride and dried.

This gives 13 g of white crystals of m.p. 180° C. (decomp.)

Yield: 82% of theory.

Example (XIII-2)

The compound of the formula

of m.p. 197° C. (decomposition) is obtained analogously to Example(XIII-1).

Yield: 91% of theory.

Example (XIII-3)

The compound of the formula

of m.p. 250° C. (decomposition) is obtained analogously to Example(XIII-1).

Yield: 53% of theory.

Example (XIV-1)

1.52 g (0.0086 mol) of 2,6-difluorobenzoyl chloride are added dropwise(at 10 to 20° C.) to a mixture of 2.5 g (0.0086 mol) of2-amino-2-phenyl-(4-difluoromethoxyphenyl)-ethanol of Example (XIII-1)and 0.9 g (0.009 mol) of triethylamine in 50 ml of THF. The mixture issubsequently stirred for 3 hours and concentrated, the product is takenup in methylene chloride, the mixture is washed three times with water,dried and reconcentrated.

This gives 3.3 g of pale beige crystals of m.p. 146° C.

Yield: 83.5% of theory.

The following compounds of the formula (XIV) are obtained analogouslyand in accordance with the general preparation instructions:

TABLE 5 (m = 0, n = 1) Yield [% of Ex. No. OR M.p. [°C.] theory] XIV-24-OCF₂CHFCl 194-195 54 XIV-3 4-OCF₂CHFCF₃ 142-145 73 XIV-4 4-OCF₂CF₂H184-186 81

Example (XVII-1)

10.6 g (0.022 mol) of hydroxyethylamide of Example (XIV-2) are suspendedin 100 ml of dry toluene. 10.5 g (0.088 mol) of thionyl chloride areadded dropwise without cooling, a clear yellow solution being formed.This is heated to 70° C. and held at this temperature for 2 hours. Aftercooling to 0° C., the mixture is filtered, and the product is washedwith a small amount of toluene and dried.

This gives 8.8 g (79% of theory) of white crystals of m.p. 190-192° C.

Example (XVII-2)

Analogously to Example XVII-I

white crystals of m.p. 161-164° C. (83% of theory) are obtained.

Example (XVII-3)

130.4 g (0.98 mol) of aluminum chloride are introduced in portions at 5°C. in the course of 30 minutes into a mixture of 53 g (0.213 mol) of2-(2,6-difluorobenzoylamido)-2-methoxy-1-chloroethane, 48.4 g (0.2 mol)of 4-ethoxycarbonyloxybiphenyl and 12 ml of glacial acetic acid in 200ml of methylene chloride. In the course of this, the color of the batchchanges via blue to a reddish violet. The reaction mixture is stirredfor 1 hour at 5° C. and for 1 hour at 10° C. and carefully poured ontoice, the suspension is carefully decanted off from water andconcentrated on a rotary evaporator, the residue is treated with 50 mlof acetonitrile, and the crystals which have precipitated are filteredoff with suction. Yield 42.8 g (47% of theory), m.p. 209° C.

The following compounds of the formula (XVII)

are obtained analogously or in accordance with the general informationon the preparation:

TABLE 6 (m = 0, n = 1) Ex. No. OR′ M.p. [° C.] (XVII-4)

125-130 (XVII-5)

225-130

Example for the use of the compound of Example (I-8)

First, 0.22 ml (0.005 mol) of 45% NaOH solution and then, at 0° C., 0.5g (0.005 mol) of ethyl bromide are added dropwise to 1.75 g of thecompound of Example (I-8) in 10 ml of dimethylformamide. The mixture isstirred for 2 hours at room temperature and poured into 50 ml ofice-water, and the crystals are filtered off with suction. The filtrateis extracted using ethyl acetate, and the ethyl acetate phase is driedand concentrated in vacuo. The crystals are combined, stirred with 20 mlof diisopropyl ester and filtered off with suction. Yield 1.1 g (58% oftheory), m.p. 148 to 150° C.

In the use examples which follow, the compound of the formula (A)

which is known from EP-A-0 432 661 was employed as comparison substance.

USE EXAMPLES Example A

Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis) while the leaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a destruction rate of 100% was caused, after 3 days, forexample by the compound of Preparation Example (I-2) at an exemplaryactive compound concentration of 0.01% and a destruction rate of 100%was caused, after 7 days, by the compound of Preparation Example I-11 atan exemplary active compound concentration of 0.1%.

Example B

Spodoptera test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1. part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the fall arrnyworm (Spodoptera frugiperda)while the leaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a destruction rate of 100% was achieved, after 7 days, forexample by the compound of Preparation Example (I-11) at an exemplaryactive compound concentration of 0.1%.

Example C

Tetranychus test (OP resistant/spray treatment)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are severely infested with allstages of the greenhouse red spider mite (Tetranychus urticae) aresprayed with an active compound preparation of the desiredconcentration.

After the specified periods of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, a destruction rate of 95% was achieved, after 14 days, forexample by the compound of Preparation Example (I-2) at an exemplaryactive compound concentration of 0.000032%, while the known compound (A)only caused a destruction rate of 80%.

Example D

Ecdysis test on polyphagous tick nymphs

Test animals: Amblyomma variegatum, nymphal stages which have suckedthemselves full

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compoundare mixed with 7 parts of the abovementioned solvent-emulsifier mixture,and the resulting emulsion concentrate is diluted with water to theconcentration desired in each case.

10 nymphs which have sucked themselves full are immersed for 1 minuteinto the preparation of active compound to be tested. The animals aretransferred to Petri dishes (Ø9.5 cm) which are equipped with filterpaper disks and covered. After the nymphs have remained in acontrol-environment cabinet for 5-6 weeks, the ecdysis rate isdetermined.

100% means that all the animals have undergone normal ecdysis; 0% meansthat none of the animals has undergone normal ecdysis.

In this test, an ecdysis rate of 0% was shown, for example, by thecompound of Preparation Example (I-2) at an exemplary active compoundconcentration of 1000 ppm.

Example E

Blowfly larvae test/development-inhibitory action

Test animals: Lucilia cuprina larvae

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compoundare mixed with 7 parts of the abovementioned solvent-emulsifier mixture,and the resulting emulsion concentrate is diluted with water to theconcentration desired in each case.

Approximately 20 Lucilia cuprina larvae are introduced into a test tubewhich contains approximately 1 cm³ of horse meat and 0.5 ml of thepreparation of active compound to be tested. After 24 and 48 hours, theeffectiveness of the preparation of active compound is determined. Thetest tubes are transferred into beakers whose bottom is covered withsand. After a further 2 days, the test tubes are removed, and the pupaeare counted.

The activity of the preparation of the active compound is assessedtaking into account the number of flies which have emerged after 1.5times the development time and an untreated control. 100% means that noflies have emerged; 0% means that all flies have emerged normally.

In this test, an activity of 100% was shown, for example, by thecompound of Preparation Example I-2 at an exemplary active compoundconcentration of 1000 ppm.

Example F

Nephotettix test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with the green rice leafhopper (Nephotettix cincticeps) whilethe seedlings are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the leafhoppers have been killed; 0% means that noneof the leafhoppers have been killed.

In this test, a destruction rate of at least 90% was caused, after 6days, for example by the compounds of Preparation Examples I-7, I-8 andI-11 at an exemplary active compound concentration of 0.1%.

It will be understood that the specification and examples areillustrative but not limitive of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. The compound of the formula (I)

in which A represents hydrogen, fluoro or chloro, B represents fluoro orchloro, R represents R¹ or R², where R¹ represents one of the groups-CHF₂, -CCIF₂, -CF₂CHFCl, CF₂CH₂F, -CF₂CHF₂CCl₃, -CF₂CHFCF₃,-CH₂CF₂CHF₂, -CH₂CF₂CF₃,

 R² represent propenyl, butenyl, pentenyl, hexenyl, propinyl, butinyl,pentinyl, or represents one of the cycloalkylalkyl groups:

 or represents the cycloalkenyalkyl group:

 or represents one of the phenylalkyl groups:

or represents

or represents the radical —COR³, R³ represents methyl, ethyl, propyl; orrepresents methoxy, ethoxy, propoxy, butoxy; or represents cyclopropyl,cyclohexyl; or represents cyclohexyloxy; or represents phenyl,2-chlorophenyl, 2,6-difluorophenyl, 2-trifluoromethoxyphenyl,4-trifluoromethoxyphenyl; 2,4-dichlorophenyl; 3,4-dichlorophenyl;represents the radical -NHR⁵, R⁵ represents methyl, ethyl, or representsphenyl which is optionally monosubstituted by chlorine, X representsfluorine, chlorine or bromine, m represents 0 or 1 and n represents 1.2. A compound according to claim 1, wherein R is R¹.
 3. A compoundaccording to claim 1, wherein such compound is


4. The compound according to claim 1, which has the formula


5. A compound according to claim 1, wherein the compound is


6. A compound according to claim 1, wherein the compound is


7. A compound according to claim 1, wherein the compound is


8. A compound


9. A compound


10. A pesticidal composition comprising a pesticidally effective amountof a compound according to claim 1 and a diluent.
 11. A method ofcombatting insects, arachnids and nematodes which comprises applying tosuch insects, arachnids and nematodes or to a locus form which it isdesired to exclude such insects, arachnids and nematodes a compoundaccording to claim 1 in an amount effective to combat such insects,arachnids and nematodes and a diluent.
 12. The method according to claim11, wherein such compound is